Журнал Сибирского федерального университета
Journal of Siberian Federal University
Химия
Chemistry
Редакционный совет:
академик РАН Е.А. Ваганов
академик РАН И.И. Гительзон
академик РАН А.Г. Дегерменджи
академик РАН В.Ф. Шабанов
чл.-корр. РАН, д-р физ.-мат. наук
В.Л. Миронов
чл.-корр. РАН, д-р техн. наук
Г.Л. Пашков
чл.-корр. РАН, д-р физ.-мат. наук
В.В. Шайдуров
чл.-корр. РАН, д-р физ.-мат. наук
В.В. Зуев
Editorial Advisory Board
Chairman:
Eugene A. Vaganov
Members:
Josef J. Gitelzon
Vasily F. Shabanov
Andrey G. Degermendzhy
Valery L. Mironov
Gennady L. Pashkov
Vladimir V. Shaidurov
Vladimir V. Zuev
Editorial Board:
Editor-in-Chief
Mikhail I. Gladyshev
Founding Editor
Vladimir I. Kolmakov
Managing Editor
Olga F. Alexandrova
Executive Editor for Chemistry
Boris N. Kuznetsov
CONTENTS / СОДЕРЖАНИЕ
Viktor F. Odyakov and Elena G. Zhizhina
Products of Homogeneous Two-Stage Oxidation of 1-Butene to
Butanone with O2
Over the Catalyst Pd + Heteropoly Acid
– 221 –
Sergey M. Zharkov, Evgeny T. Moiseenko,
Roman R. Altunin and Galina M. Zeer
In situ transmission electron microscopy and electron diffraction
investigation of solid-state reactions and atomic ordering in
Cu/Au bilayer nanofilms
– 230 –
В.И. Шарыпов, Н.Г. Береговцова,
С.В. Барышников, Б.Н. Кузнецов,
À.Â. Восьмериков, Î.Ï. Òàðàí, Â.Å. Агабеков
Šе!м,че“*= *%…"е!“, л,г…,…= д!е"е“,…/ %“,…/ " .2=…%ле
" C!,“32“2",, це%л,2…/. *=2=л,ƒ=2%!%"
– 241 –
Ò.Ã. Øåíäðèê, Â.À. Кучеренко, Â.Â. Симонова
j%…"е!“,
3гле!%д“%де!›=?,. %2.%д%" " ›,д*,е C!%д3*2/
– 251 –
Fe, Mn, Co, Ni) дл гл3K%*%г% ›,д*%-=ƒ…%г% %*,“ле…,
-е…%л= Cе!%*“,д%м "%д%!%д=
Î.Ï. Òàðàí, À.Á. Àþøååâ, Î.Ë. Огородникова,
И.П. Просвирин, Л.А. Исупова
oе!%"“*,2%C%д%K…/е *=2=л,ƒ=2%!/ 2,C= LaBO3
– 266 –
Редактор И.А. Вейсиг Корректор Е.Г. Иванова
Компьютерная верстка Е.В. Гревцовой
Подписано в печать 19.09.2013 г. Формат 84х108/16. Усл. печ. л. 8,85.
Уч.-изд. л. 8,35. Бумага тип. Печать офсетная. Тираж 1000 экз. Заказ 3135.
Отпечатано в ПЦ БИК СФУ. 660041 Красноярск, пр. Свободный, 82a.
.,м,че“*, м%д,-,ц,!%"=……/. 3глеL ,
2013 6 (3)
(B = Cu,
Стр.1
Editorial board for Chemistry:
Boris Kuznetsov – Series Editor, Professor, Siberian
Federal University
Nikolai Chesnokov – Associate Editor, Siberian Federal
University
Lyubov Altunina – Professor, Institute of Petroleum
Chemistry, Russian Academy of Sciences, Siberian
Branch
Natalia Bazarnova – Professor, Altai State University
Vasili Babkin – Professor, Favorsky Irkutsk Institute of
Chemistry, Russian Academy of Sciences, Siberian
Branch
Vicente Cebolla – Instituto de Carboquimica, CSIC,
Spain
Viktor Denisov – Professor, Siberian Federal University
Zinfer Ismagilov – Professor, Institute of Coal
Chemistry and Material Science, Russian Academy
of Sciences, Siberian Branch
Sergey Kachin – Professor, Siberian Federal University
Sergey Kirik – Professor, Siberian Federal University
Catherine Pinel – Professor, IRCELYON, Lyon, France
Alan Celzard – Professor, Institut Jean Lamour, Epinal,
France
Vladimir Likholobov – Corresponding Member RAS,
Institute of Hydrocarbons Processing, Russian
Academy of Sciences, Siberian Branch
Yury Mikhlin – Professor, Siberian Federal University
Gennady Pashkov – Professor, Siberian Federal
University
Anatoly Rubailo – Professor, Siberian Federal
University
Tatyana Ryazanova – Professor, Siberian Sate
Technological University
Vladimir Sobyanin – Professor, Boreskov Institute of
Catalysis, Russian Academy of Sciences, Siberian
Branch
Valery Tarabanko – Professor, Institute of Chemistry
and Chemical Technology, Russian Academy of
Sciences, Siberian Branch
Tatiana Shendrik – Professor, Litvinenko Institute of
Physical Organic Chemistry and Coal Chemistry,
Ukraine
Á.Í. Êóçíåöîâ, Í.Â. ×åñíîêîâ,
Н.В. Гарынцева, О.В. Яценкова
h…2ег!,!%"=……=
*=2=л,2,че“*=
Cе!е!=K%2*=
д!е"е“,…/ %“,…/ " ›,д*,е , 2"е!д/е K,%2%Cл,"=
– 286 –
Ë.Ò. Äåíèñîâà, Ë.Ã. ×óìèëèíà, Â.Ì. Денисов
ŠеCл%ем*%“2ь %*“,д…/. “%ед,…е…,L “,“2ем %*“,д
K=!, $ %*“,д ›елеƒ= , %*“,д *=льц, $ %*“,д
",“м32=
– 299 –
Â.È. Êóçüìèí, Ä.Â. Êóçüìèí, À.Ì. Жижаев
hƒ3че…,е "е?е“2"е……%г% “%“2="= , 2е.…%л%г,че“*,.
“"%L“2" !ед*%ме2=лль…/. !3д )3*23*%…“*%г%
ме“2%!%›де…,
– 303 –
Ë.Ã. Бондарева, À.Ñ. Æóê, Â.Â. Сурсякова,
À.È. Ðóáàéëî, Í.È. Òàíàíàåâ, È.Ã. Тананаев
u,м,*%-.*%л%г,че“*%е “%“2% …,е !=L%…= г. hг=!*=
j!=“…% !“*%г% *!=
– 313 –
Þ.À. Òþëüêîâà, Ò.Â. Ðÿçàíîâà,
Î.Í. Åðåìåíêî, Ñ.Â. Ушанов
l%дел,!%"=…,е C!%це““= .*“2!=*ц,, *%!/ “%“…/
"%д…%-?ел%ч…/м !=“2"%!%м
– 321 –
Свидетельство о регистрации СМИ
ПИ № ФС77-28-726 от 29.06.2007 г.
Серия включена в «Перечень ведущих рецензируемых
научных журналов и изданий, в которых
должны быть опубликованы основные
научные результаты диссертации на соискание
ученой степени доктора и кандидата наук» (редакция
2010 г.)
Стр.2
Journal of Siberian Federal University. Chemistry 3 (2013 6) 221-229
~ ~ ~
УДК 547.313.4 : 542.943-92’7.002.67
Products of Homogeneous Two-Stage Oxidation
of 1-Butene to Butanone with O2
the Catalyst Pd + Heteropoly Acid
Over
Viktor F. Odyakov and Elena G. Zhizhina*
Boreskov Institute of Catalysis,
5 Lavrentieva, Novosibirsk, 630090 Russia
Received 27.04.2013, received in revised form 18.06.2013, accepted 24.08.2013
Oxidation of 1-butene to butanone in the presence of homogeneous catalyst Pd + HPA (H12
followed by regeneration of the catalyst with O2
process are acetic acid (1.4 %) and condensed compounds С7
–C8
are completely oxidized to CO2
О2
, С8
Н14
О2
, С6
Н6
О2
(total 1.1 %). In the course of the catalyst regeneration at 170 °С under O2
C6
P3
Mo18
V7
, and С8
O85
Н10
)
proceeds with selectivity 97.5 %. Side products of the
Н12
and acetic acid. n-Butanal is absent in the reaction products,
that permits readily to separate butanone as a water azeotrope from the reduced catalyst.
Keywords: Oxidation of 1-butene to butanone, homogeneous
products.
The processes of oxidation of lower alkenes C2
reaction (1) are of great practical importance:
CH2=CHR + 1/2 O2
, or C2
Here R = H, CH3
H5
Introduction
–C4
cat CH3COR.
a homogeneous catalyst, which was an aqueous solution of PdCl2
[1, 2]. CuCl2
to carbonyl compounds with dioxygen by
(1)
. In the late 1950s the Wacker company had suggested for such processes
+ CuCl2
(ca. 2 % [3]) < C3
(ca. 4 %) < C4
here is a
reversible oxidant, which reduced form is readily oxidized with dioxygen. Such catalyst had a high
concentration of chlorides (up to 2 M), that led to formation of toxic chloroorganic side products.
Their amount strongly increased in the series C2
(> 6 %) [2, 4].
Amount of chloroorganics strongly increased also at elevated temperature [4] but decreased after
dehydrochlorination (see later). Besides, various amounts of aldehydes, RCH2
together with ketones, CH3
COR. When propene or 1-butene were oxidized, yield of RCH2
CHO, were formed
CHO varied
from 3 to 18 % [2, 5]. Only in oxidation of 2-butene, butanone was the single reaction product [1]. Now
© Siberian Federal University. All rights reserved
* Corresponding author E-mail address: zhizh@catalysis.ru
# 221 #
catalyst Pd + HPA, reaction
О2
pressure, the compounds
Стр.3